WO2017061514A1 - Matière d'électrode négative, électrode négative, et batterie rechargeable au lithium-ion - Google Patents

Matière d'électrode négative, électrode négative, et batterie rechargeable au lithium-ion Download PDF

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Publication number
WO2017061514A1
WO2017061514A1 PCT/JP2016/079704 JP2016079704W WO2017061514A1 WO 2017061514 A1 WO2017061514 A1 WO 2017061514A1 JP 2016079704 W JP2016079704 W JP 2016079704W WO 2017061514 A1 WO2017061514 A1 WO 2017061514A1
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negative electrode
auxiliary agent
diameter
conductive auxiliary
active material
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PCT/JP2016/079704
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English (en)
Japanese (ja)
Inventor
利絵 寺西
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積水化学工業株式会社
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Priority to EP16853668.8A priority Critical patent/EP3361537A4/fr
Priority to JP2017544206A priority patent/JP6871167B2/ja
Publication of WO2017061514A1 publication Critical patent/WO2017061514A1/fr

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/134—Electrodes based on metals, Si or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/386—Silicon or alloys based on silicon
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention relates to a negative electrode material suitable for a lithium ion secondary battery, a negative electrode using the negative electrode material, and a lithium ion secondary battery including the negative electrode.
  • the present application claims priority based on Japanese Patent Application No. 2015-198840 filed in Japan on October 5, 2015, the contents of which are incorporated herein by reference.
  • a lithium ion secondary battery includes a positive electrode, a negative electrode, and an electrolyte.
  • the positive electrode and the negative electrode for example, an electrode having an electrode active material layer formed by applying a composition containing an electrode active material, a conductive additive and a binder to a current collector is used.
  • the electrode active material is an important factor related to the battery capacity
  • the negative electrode active material for example, graphite (graphite), silicon, silicon oxide or the like is used.
  • Patent Document 1 states that the battery capacity and the like of the battery are improved by the coexistence of fibrous carbon with the active material.
  • This invention is made
  • a negative electrode material containing a negative electrode active material, a conductive additive and a binder wherein the conductive additive includes a conductive additive A and a conductive additive B, and the conductive additive B has a diameter of 2 nm or more and less than 100 nm.
  • the conductive auxiliary agent A is fibrous carbon having an aspect ratio (A) of 1 to 10000 expressed by (length / diameter) having a diameter of 1 nm to 1000 nm, and the conductive auxiliary agent A is linear.
  • the aspect ratio (B) is larger than the aspect ratio (A)
  • the diameter of the conductive auxiliary agent A is larger than the diameter of the conductive auxiliary agent B
  • the negative electrode active The substance has a particulate shape (the negative electrode active material A negative electrode material having a ratio ⁇ expressed by (average particle diameter of the above / length of the conductive additive B) of 0.15 to 10.
  • a negative electrode material including a negative electrode active material, a conductive additive and a binder, wherein the conductive additive includes a conductive additive A and a conductive additive B, and the conductive additive B has a diameter of 2 nm or more and less than 100 nm.
  • the conductive auxiliary agent A is fibrous carbon having an aspect ratio (A) of 10 to 10,000 in a diameter of 1 nm to 1000 nm and represented by (length / diameter).
  • the aspect ratio (B) is larger than the aspect ratio (A)
  • the diameter of the conductive auxiliary agent A is larger than the diameter of the conductive auxiliary agent B
  • the negative electrode active The substance has a particulate shape, (the negative electrode active material
  • a ratio ⁇ expressed by (average particle diameter of the negative electrode active material / diameter of the conductive auxiliary agent B) is 10 to 2000, and (average particle diameter of the negative electrode active material / conductive auxiliary agent A of The ratio ⁇ represented by (diameter) is 1 to 500, and the ratio ⁇ represented by (average particle diameter of the negative electrode active material / length of the conductive auxiliary agent A) is 0.1 to 10, [ The negative electrode material according to [1] or [2].
  • the ratio ⁇ represented by (average particle diameter of the negative electrode active material / diameter of the conductive auxiliary agent B) is 10 to 2000, and (average particle diameter of the negative electrode active material / conductivity of the conductive auxiliary agent A)
  • the ratio ⁇ expressed by (diameter) is 7 to 500, and the ratio ⁇ expressed by (average particle diameter of the negative electrode active material / length of the conductive auxiliary agent A) is 0.2 to 10. 3].
  • the negative electrode active material is a compound represented by the general formula SiO z (wherein z is any number from 0.5 to 1.5), [1] to [5] The negative electrode material according to any one of the above. [7] A negative electrode in which a negative electrode active material layer formed using the negative electrode material according to any one of [1] to [6] is provided on a current collector.
  • a negative electrode comprising an active material layer containing a negative electrode active material, a conductive auxiliary agent and a binder, and a current collector, wherein the conductive auxiliary agent contains a conductive auxiliary agent A and a conductive auxiliary agent B, and the conductive auxiliary agent B is a fibrous carbon having a diameter of 2 nm or more and less than 100 nm and an aspect ratio (B) represented by (length / diameter) of 30 to 10,000, and the conductive auxiliary agent B is different from the conductive auxiliary agent A.
  • the conductive auxiliary agent A is a fibrous carbon having a diameter of 1 nm to 1000 nm and an aspect ratio (A) represented by (length / diameter) of 1 to 10,000.
  • the conductive auxiliary agent A has a straight line or a shape close to a straight line, the aspect ratio (B) is larger than the aspect ratio (A), and the conductive auxiliary agent A has a diameter of the conductive auxiliary agent B.
  • the negative electrode active material has a particulate shape.
  • a ratio ⁇ expressed by (average particle diameter of the negative electrode active material / length of the conductive additive B) is 0.15 to 10.
  • a negative electrode comprising an active material layer containing a negative electrode active material, a conductive auxiliary agent and a binder, and a current collector
  • the conductive auxiliary agent comprises a conductive auxiliary agent A and a conductive auxiliary agent B
  • the conductive auxiliary agent B is a fibrous carbon having a diameter of 2 nm or more and less than 100 nm and an aspect ratio (B) represented by (length / diameter) of 30 to 10,000
  • the conductive auxiliary agent B is different from the conductive auxiliary agent A.
  • the conductive auxiliary agent A is a fibrous carbon having a diameter of 1 nm to 1000 nm and an aspect ratio (A) of 10 to 10,000 expressed by (length / diameter).
  • the conductive auxiliary agent A has a straight line or a shape close to a straight line, the aspect ratio (B) is larger than the aspect ratio (A), and the conductive auxiliary agent A has a diameter of the conductive auxiliary agent B. Larger than the diameter, the negative electrode active material has a particulate shape.
  • a ratio ⁇ expressed by (average particle diameter of the negative electrode active material / diameter of the conductive auxiliary agent B) is 10 to 2000, and (average particle diameter of the negative electrode active material / conductive auxiliary agent A of The ratio ⁇ represented by (diameter) is 1 to 500, and the ratio ⁇ represented by (average particle diameter of the negative electrode active material / length of the conductive auxiliary agent A) is 0.1 to 10, [ 8] or the negative electrode according to [9].
  • a ratio ⁇ expressed by (average particle diameter of the negative electrode active material / diameter of the conductive auxiliary agent B) is 10 to 2000, and (average particle diameter of the negative electrode active material / conductivity of the conductive auxiliary agent A)
  • the ratio ⁇ expressed by (diameter) is 7 to 500, and the ratio ⁇ expressed by (average particle diameter of the negative electrode active material / length of the conductive auxiliary agent A) is 0.2 to 10.
  • the negative electrode active material is a compound represented by the general formula SiO z (wherein z is any number from 0.5 to 1.5), [8] to [12] The negative electrode according to any one of the above. [14] A lithium ion secondary battery comprising the negative electrode according to any one of [7] to [13].
  • a lithium ion secondary battery having a high capacity development rate and a high capacity maintenance rate is provided.
  • 1st embodiment of the negative electrode material of this invention is a negative electrode material containing a negative electrode active material, the conductive support agent A, the conductive support agent B, and a binder.
  • the negative electrode active material of the present embodiment is the same as the negative electrode active material used in the conventional lithium ion secondary battery, but increases the contact efficiency between the conductive auxiliary agent A and the conductive auxiliary agent B and the negative electrode active material.
  • the average particle diameter average particle diameter which is the size of the negative electrode active material.
  • the average particle size X of the negative electrode active material of the present embodiment satisfies all of the following (i) to (iv).
  • the ratio ⁇ expressed by the average particle diameter X of the negative electrode active material / the diameter of the conductive additive B is 10 to 2000.
  • the ratio ⁇ represented by the average particle diameter X of the negative electrode active material / the diameter of the conductive additive A is 1 to 500.
  • the ratio ⁇ expressed by the average particle diameter X of the negative electrode active material / the length of the conductive additive B is 0.15 to 10.
  • the ratio ⁇ expressed by the average particle diameter X of the negative electrode active material / the length of the conductive additive A is 0.1 to 10.
  • the conductive auxiliary agent B of the present embodiment is fibrous carbon having an aspect ratio (B) of 30 to 10000 expressed in length / diameter and having a diameter of 2 nm or more and less than 100 nm, and the conductive auxiliary agent B is the conductive auxiliary agent B. It has a non-linear shape different from agent A.
  • the conductive auxiliary agent A of this embodiment is fibrous carbon having an aspect ratio (A) of 1 to 10000 expressed in length / diameter and having a diameter of 1 nm to 1000 nm, and the conductive auxiliary agent A is linear or linear. It has a shape close to.
  • the diameters of the conductive assistants A and B mean the average outer diameter (average fiber diameter) in a cross section orthogonal to the longitudinal direction of the respective conductive assistants.
  • the conductive auxiliary agent B is a carbon material that contributes to conduction over a relatively long distance in the negative electrode material, and since it is easy to take a rigid linear shape, it is a carbon material that has a relatively low contact probability with the negative electrode active material.
  • the conductive auxiliary material A is a carbon material that contributes to conduction over a relatively short distance in the negative electrode material, and it is easy to take an agglomerated pill shape, so that the contact probability with the negative electrode active material and conductive auxiliary agent B in the vicinity is high. It is a carbon material.
  • the aspect ratio (B) of the conductive additive B is preferably larger than the aspect ratio (A) of the conductive additive A.
  • the conductivity of the negative electrode material by the conductive additive B can be further increased.
  • the diameter of the conductive auxiliary agent A is preferably larger than the diameter of the conductive auxiliary agent B.
  • the ratio value of (the diameter of conductive auxiliary agent A / the diameter of conductive auxiliary agent B) is preferably 1.1 to 100. 2 to 50 is more preferable, and 5 to 50 is more preferable.
  • the ratio of the diameter and the length of the conductive auxiliary agent A and the conductive auxiliary agent B is in the above relationship with respect to the average particle diameter X of the negative electrode active material, thereby improving the conductivity in the negative electrode material, Battery performance can be improved.
  • the ratio ⁇ is preferably 10 to 2000, more preferably 50 to 1500, and still more preferably 80 to 1000.
  • the ratio ⁇ is preferably 1 to 500, more preferably 5 to 500, and still more preferably 7 to 500.
  • the value of the ratio ⁇ exceeds 2
  • 1 to 180 is preferable
  • 2 to 120 is more preferable
  • 4 to 80 is more preferable.
  • the ratio ⁇ is preferably 0.15 to 10, more preferably 0.16 to 8, and further preferably 0.18 to 3.
  • the ratio ⁇ is preferably 0.1 to 10, more preferably 0.15 to 9, and further preferably 0.18 to 8.
  • the ratio ⁇ is 0.15 or more, it is possible to improve the conductivity between materials that are not in contact with each other among the active material, the conductive additive B, the current collector, and the like.
  • the ratio ⁇ is 10 or less, the surface smoothness of the active material layer is easily obtained when the active material layer is formed.
  • the content ratio of the negative electrode active material to the total mass of the negative electrode active material, the conductive auxiliary agent A, the conductive auxiliary agent B, the particulate conductive auxiliary agent and the binder described later is 40 to 85% by mass. It is preferable that it is 55 to 80% by mass.
  • the content ratio of the negative electrode active material is 40% by mass or more, the discharge capacity of the lithium ion secondary battery is further improved, and when the content ratio of the negative electrode active material is 85% by mass or less, the negative electrode structure is stably maintained. It becomes easy.
  • a silicon oxide is mentioned, for example.
  • the silicon oxide include those represented by the general formula “SiO z (wherein z is any number from 0.5 to 1.5)”.
  • SiO z is any number from 0.5 to 1.5
  • this SiO is amorphous SiO, or around the Si of the nanocluster so that the molar ratio of Si: SiO 2 is about 1: 1.
  • This is a composite of Si and SiO 2 in which SiO 2 exists. SiO 2 is presumed to have a buffering action against the expansion and contraction of Si during charging and discharging.
  • the silicon oxide is preferably in the form of particles.
  • the average particle diameter is preferably 30 ⁇ m or less, more preferably 20 ⁇ m or less, particularly preferably 10 ⁇ m or less, and most preferably 5 ⁇ m or less. .
  • silicon oxide having the above average particle diameter is used, the effect of the combined use with the conductive auxiliary agents A and B can be obtained more remarkably.
  • Examples of a method for adjusting the average particle diameter of silicon oxide to a desired value include a method of pulverizing by a known method using a ball mill or the like.
  • the average particle diameter of silicon oxide for example, using an electron microscope, the particle diameter of about 100 arbitrary silicon oxide particles used in the negative electrode material is measured, and the average value is calculated and obtained. A method is mentioned.
  • the content ratio of the conductive auxiliary agent A to the total mass of the negative electrode active material, the conductive auxiliary agent A, the conductive auxiliary agent B, the particulate conductive auxiliary agent and the binder described later is 1 to 15% by mass. Preferably, it is 2 to 8% by mass.
  • the content ratio of the conductive auxiliary agent A is 1% by mass or more, the conductivity between the conductive auxiliary agents A and B constituting the negative electrode material and the negative electrode active material is further improved, and the content ratio of the conductive auxiliary agent A is 15% by mass.
  • the content is less than or equal to%, the dispersibility of each material in the negative electrode material is increased, and the conductivity is further improved.
  • the conductive additive A is preferably substantially linear, that is, a straight line or a shape close to a straight line.
  • the lower limit of the aspect ratio (A) represented by the length (average fiber length) / diameter (average fiber diameter) of the conductive additive A is, for example, preferably 1 or more, and more preferably 2 or more. 3 or more is more preferable, and 5 or more is more preferable.
  • the upper limit is preferably 10,000 or less, more preferably 5000 or less, still more preferably 1000 or less, and even more preferably 600 or less. Yes.
  • the aspect ratio (A) is 1 or more, the contact efficiency between the conductive additive A and other conductive material, active material, or current collector is increased, and the conductivity of the negative electrode material is improved.
  • the aspect ratio (A) is 10,000 or less, the dispersibility of the conductive auxiliary agent A in the negative electrode material is increased, and the conductivity of the negative electrode material is further improved. Moreover, when the active material layer is formed, the surface smoothness of the active material layer is easily obtained.
  • the ratio (m1 / m2) of the mass m1 of the negative electrode active material and the mass m2 of the conductive additive A contained in the negative electrode material of this embodiment is preferably 1 to 30, for example, and 10 to 20. Is more preferable.
  • the mass ratio is 1 or more, the dispersibility of the conductive additive A in the negative electrode material is increased, and the conductivity of the negative electrode material is further improved.
  • the mass ratio is 30 or less, the contact efficiency between the conductive additive A and the negative electrode active material is increased, and the conductivity of the negative electrode material is further improved.
  • the conductive additive A contributes to the improvement of conductivity by forming a bridge-like network structure in the negative electrode material. It is also presumed that it contributes to the structural stabilization of the negative electrode material.
  • the average fiber diameter as the diameter of the conductive additive A is preferably 1 nm or more and 1000 nm or less, more preferably 3 nm or more and 500 nm or less, and further preferably 7 nm or more and 250 nm or less.
  • the diameter of the conductive auxiliary agent A is 1 nm or more, the negative electrode material has rigidity enough to maintain the form as fibrous carbon.
  • the diameter of the conductive auxiliary agent A is 1000 nm or less, even if the addition amount (added weight) is small, the contact probability with the negative electrode active material and the conductive auxiliary agent B in the vicinity can be further increased.
  • the average fiber length as the length of the conductive auxiliary agent A is preferably 0.1 ⁇ m to 30 ⁇ m, and more preferably 0.5 ⁇ m to 20 ⁇ m.
  • the length of the conductive auxiliary agent A is 0.1 ⁇ m or more, it is easy to obtain rigidity for maintaining a length that contributes to relatively long-distance conduction.
  • the length of the conductive auxiliary agent A is 30 ⁇ m or less, the uniformity of the distribution of the active material, the conductive auxiliary agent B and the like in the negative electrode can be improved.
  • the fiber diameter of the conductive auxiliary agent A As a method for measuring the average fiber diameter of the conductive auxiliary agent A, for example, using an electron microscope, the fiber diameter is measured for about 100 arbitrary conductive auxiliary agents A used for the negative electrode material, and the average value is calculated. The method to ask for is mentioned. Similarly, as a method of measuring the average fiber length of the conductive auxiliary agent A, for example, using an electron microscope, the fiber length is measured for about 100 arbitrary conductive auxiliary agents A used for the negative electrode material, and the average value is obtained. The method of calculating is mentioned.
  • Examples of the conductive additive A of the present embodiment include carbon nanotubes (CNT).
  • the CNT may be a single layer or a multilayer.
  • As the conductive auxiliary agent A one kind may be used alone, or two or more kinds may be used in combination.
  • the content ratio of the conductive auxiliary agent B to the total mass of the negative electrode active material, the conductive auxiliary agent A, the conductive auxiliary agent B, the particulate conductive auxiliary agent described later and the binder is 1 to 15% by mass. Preferably, it is 2 to 8% by mass.
  • the content ratio of the conductive auxiliary agent B is 1% by mass or more, the conductivity between the conductive auxiliary agents A and B constituting the negative electrode material and the negative electrode active material is further improved, and the content ratio of the conductive auxiliary agent B is 15% by mass.
  • the content is less than or equal to%, the dispersibility of each material in the negative electrode material is increased, and the conductivity is further improved.
  • the conductive auxiliary agent B has a non-linear shape different from that of the conductive auxiliary agent A, and is preferably made of a material that tends to be a non-linear bent structure.
  • the bent structure means that the structure is not substantially linear, and has a bent structure, a helical structure, etc., and a structure with low regularity of shape.
  • the conductive auxiliary agent B has a large aspect ratio, for example, it becomes easy to take a pill shape in which a plurality of conductive auxiliary agents B aggregate.
  • the conductive auxiliary agent B has such a low regularity shape, it is possible to increase the number of contacts between the conductive auxiliary agent B and the active material, the conductive auxiliary agent A, or the current collector.
  • the conductive auxiliary agent B since the conductive auxiliary agent B has such a bent structure and a shape with low regularity, it is possible to suppress the decrease in the contact point due to the temperature change or the volume change of the active material or the like accompanying charge / discharge.
  • the aspect ratio (B) represented by the length (average fiber length) / diameter (average fiber diameter) of the conductive additive B is, for example, preferably 30 or more, more preferably 50 or more, and 150 More preferably, it is more preferably 300 or more.
  • the upper limit is preferably 10,000 or less, more preferably 5000 or less, and even more preferably 1000 or less.
  • the aspect ratio (B) is 30 or more, the contact efficiency between the conductive additive B and another conductive material or active material is increased, and the conductivity of the negative electrode material is improved.
  • the aspect ratio (B) is 10,000 or less, the dispersibility of the conductive auxiliary agent B in the negative electrode material is increased, and the conductivity of the negative electrode material is further improved.
  • the ratio (m1 / m3) of the mass m1 of the negative electrode active material and the mass m3 of the conductive additive B contained in the negative electrode material of this embodiment is preferably 4 to 40, for example, and 5 to 30. Is more preferable, and 6 to 20 is more preferable.
  • the mass ratio is 4 or more, the contact efficiency between the conductive additive B and the negative electrode active material is increased, and the conductivity of the negative electrode material is further improved.
  • the mass ratio is 40 or less, the dispersibility of the conductive additive B in the negative electrode material is increased, and the conductivity of the negative electrode material is further improved.
  • the conductive auxiliary agent B contributes to improving the conductivity of the negative electrode material by filling the inside of the bridge-like network structure formed by the conductive auxiliary agent A in the negative electrode material, and also to stabilize the structure of the negative electrode material. Presumed to have contributed.
  • the conductive auxiliary agent B is located along the surface of the conductive auxiliary agent A, the active material, or the current collector in the negative electrode material, and an electrical contact is generated, thereby improving the conductivity of the negative electrode material. Presumed to have contributed.
  • the average fiber diameter as the diameter of the conductive auxiliary agent B is preferably 2 nm or more and less than 100 nm, more preferably 5 nm or more and 50 nm or less, and further preferably 10 nm or more and 30 nm or less.
  • the diameter of the conductive auxiliary agent B is 2 nm or more, it becomes possible to keep the conductivity by following the volume change of the negative electrode active material accompanying charge / discharge.
  • the diameter of the conductive auxiliary agent B is less than 100 nm, it is possible to prevent the rigidity from becoming excessively high and to increase the flexibility for easily coming into contact with other conductive materials constituting the negative electrode material.
  • the average fiber length as the length of the conductive additive B is preferably 0.1 ⁇ m to 100 ⁇ m, and more preferably 0.2 ⁇ m to 30 ⁇ m.
  • the length of the conductive auxiliary agent B is 0.1 ⁇ m or more, suitable physical properties as fibrous carbon are easily obtained.
  • the length of the conductive auxiliary agent B is 100 ⁇ m or less, the uniformity of the distribution of the active material, the conductive auxiliary agent B and the like in the negative electrode can be improved, and the capacity expression rate described later can be increased. Further, the contact property with other conductive materials constituting the negative electrode material can be enhanced.
  • the fiber diameter of the conductive auxiliary agent B is measured for about 100 arbitrary conductive auxiliary agents B used for the negative electrode material, and the average value is calculated. The method to ask for is mentioned.
  • the fiber length of the conductive auxiliary agent B is measured for about 100 arbitrary conductive auxiliary agents B used for the negative electrode material, and the average value is obtained. The method of calculating is mentioned.
  • Examples of the conductive additive B of the present embodiment include carbon fibers and carbon nanotubes (CNT).
  • the CNT may be a single layer or a multilayer.
  • As the conductive auxiliary agent B one kind may be used alone, or two or more kinds may be used in combination.
  • the negative electrode material of this embodiment contains a particulate conductive auxiliary that does not correspond to the negative electrode active material, the conductive auxiliary A, and the conductive auxiliary B.
  • the particulate conductive additive can contribute to the improvement of the conductivity of the negative electrode material by expanding the contact area between the conductive materials in the negative electrode material.
  • the particulate conductive additive is not an essential component and is added as necessary.
  • the content ratio of the particulate conductive additive to the total mass of the negative electrode active material, conductive additive A, conductive additive B, particulate conductive additive and binder is 1 to 20% by mass. It is preferably 5 to 15% by mass.
  • the content ratio of the particulate conductive auxiliary is 1% by mass or more, the conductive materials constituting the negative electrode material are electrically connected to each other via the particulate conductive auxiliary agent, thereby further improving the conductivity of the negative electrode material. be able to.
  • the content ratio of the particulate conductive auxiliary is 20% by mass or less, it is possible to prevent the dispersion of the conductive auxiliary necessary for short-distance or long-distance conduction by the conductive auxiliary agents A and B in the negative electrode material.
  • suitable particulate conductive assistants in the present embodiment include carbon blacks such as acetylene black and ketjen black; graphite (graphite); fullerenes and the like.
  • the average particle diameter of the particulate conductive additive is preferably 10 to 100 nm, and more preferably 15 to 60 nm.
  • the structure of the particulate conductive additive is preferably a structure in which the particles are connected to each other like a daisy chain.
  • the conductivity of the negative electrode material can be further improved by the combined use with the conductive auxiliary A and B. Adjustment and measurement of the average particle size of the particulate conductive additive can be performed in the same manner as in the case of the average particle size of silicon oxide described above.
  • One type of particulate conductive auxiliary may be used alone, or two or more types may be used in combination.
  • the ratio (m1 / m4) of the mass m4 of the particulate conductive additive to the mass m1 of the negative electrode active material is preferably 1 to 20, and more preferably 3 to 15. .
  • the content is in the above range, the above-described effects due to the inclusion of the particulate conductive additive can be obtained more remarkably.
  • the content of the binder is preferably 3 to 30% by mass with respect to the total mass of the negative electrode active material, the conductive auxiliary agent A, the conductive auxiliary agent B, the particulate conductive auxiliary agent and the binder. More preferably, it is 5 to 20% by mass.
  • the structure of a negative electrode material is maintained more stably as the content rate of a binder is 3 mass% or more, and discharge capacity improves more because the content rate of a binder is 30 mass% or less.
  • the binder in the present embodiment is not particularly limited, and a binder used for a negative electrode of a conventional lithium ion secondary battery is applicable.
  • a binder used for a negative electrode of a conventional lithium ion secondary battery is applicable.
  • SBR styrene butadiene rubber
  • PAA polyacrylic acid
  • PAALi polyacrylic acid Lithium
  • PVDF polyvinylidene fluoride
  • PVDF-HFP polyvinylidene fluoride-hexafluoropropylene copolymer
  • PVA polyvinyl alcohol
  • PEO polyethylene oxide
  • PEG polyethylene glycol
  • CMC carboxymethyl cellulose
  • PAN polyacrylonitrile
  • PI polyimide
  • a binder may be used individually by 1 type and 2 or more types may be used together.
  • the negative electrode material of this embodiment may further contain other optional components not corresponding to these.
  • An example of the optional component includes a solvent for dissolving or dispersing each material constituting the negative electrode material.
  • the negative electrode material in which a solvent as an optional component is blended is preferably a liquid composition having fluidity at the time of use for producing a negative electrode to be described later.
  • the said solvent is not specifically limited, For example, water and an organic solvent are mentioned.
  • the organic solvent include alcohols such as methanol, ethanol, 1-propanol and 2-propanol; linear or cyclic amides such as N-methylpyrrolidone (NMP) and N, N-dimethylformamide (DMF); acetone and the like Of ketones.
  • NMP N-methylpyrrolidone
  • DMF N, N-dimethylformamide
  • acetone and the like Of ketones acetone and the like Of ketones.
  • 1 type may be used independently and 2 or more types may be used together.
  • the blending amount of the solvent in the liquid composition is not particularly limited, and is appropriately adjusted according to the purpose.
  • the liquid composition has a viscosity suitable for coating. What is necessary is just to adjust the compounding quantity of a solvent.
  • a blend in which the content ratio of the solvent with respect to the total mass of the liquid composition is preferably 20 to 95% by mass, more preferably 50 to 80% by mass.
  • the content ratio of the solid component with respect to the total mass of the blended component other than the solvent in the negative electrode material is preferably 10% by mass or less, and preferably 5% by mass or less. It is more preferable that
  • the negative electrode material of this embodiment can be prepared by blending a negative electrode active material, a conductive auxiliary agent A, a conductive auxiliary agent B, a particulate conductive auxiliary agent and a binder, and optional components as necessary. It is preferable that the respective components are sufficiently mixed and uniformly dispersed during the production of the negative electrode material. When mixing each component, you may mix, adding each component sequentially, and may mix all the components collectively.
  • the solvent when the solvent is blended as an optional component, the solvent may be added alone and mixed, or the solvent may be premixed with any solid component and mixed simultaneously with the blending of the solid component.
  • the mixing method of each component is not particularly limited, and examples thereof include known mixing methods using a stirrer, a stirring blade, a ball mill, a stirrer, an ultrasonic disperser, an ultrasonic homogenizer, a self-revolving mixer, and the like. What is necessary is just to set suitably mixing conditions, such as mixing temperature and mixing time, according to various methods. For example, the temperature during mixing can be set to 10 to 50 ° C., and the mixing time can be set to 3 to 40 minutes.
  • the solvent can be removed by drying, vaporization, distillation, etc., and used as a more stable negative electrode material.
  • ⁇ Negative electrode> 1st embodiment of the negative electrode of this invention is a negative electrode by which the negative electrode active material layer formed using the negative electrode material mentioned above is equipped on the electrical power collector.
  • the negative electrode active material layer constituting the negative electrode of this embodiment is preferably predoped with lithium.
  • the current collector is not particularly limited, and a current collector used in a conventional lithium ion secondary battery is applicable.
  • a current collector having conductivity such as copper, aluminum, titanium, nickel, stainless steel, etc. Is mentioned.
  • the shape of the current collector is preferably a sheet shape, and the thickness thereof can be, for example, 5 to 20 ⁇ m.
  • the thickness of the negative electrode active material layer is not particularly limited, and is preferably 5 to 100 ⁇ m, for example, and more preferably 10 to 60 ⁇ m.
  • the method for forming the negative electrode active material layer is not particularly limited.
  • the negative electrode material as a liquid composition in which the above-described solvent is blended is coated on the current collector, and the solvent is further dried to collect the current.
  • a negative electrode active material layer having a desired thickness can be formed on the body.
  • Examples of the coating method of the liquid composition include a method using various coaters such as a bar coater, a gravure coater, a comma coater, and a lip coater; a doctor blade method; a dipping method and the like.
  • the method for drying the solvent is not particularly limited, and can be performed by a known method under normal pressure or reduced pressure.
  • the drying temperature is not particularly limited, and can be set to 40 to 180 ° C., for example.
  • the drying time is not particularly limited, and can be set to 12 to 48 hours, for example.
  • a method for installing the negative electrode active material layer for example, a method in which the negative electrode active material layer is directly formed on the current collector and crimped as necessary, a method in which the negative electrode active material layer is formed on another substrate, and then moved onto the current collector to collect the current.
  • a method of pressure bonding on an electric body can be used.
  • the negative electrode of the present embodiment is preferably predoped with lithium. By pre-doping, it reacts irreversibly with silicon dioxide in the negative electrode active material layer to produce lithium silicate (Li 4 SiO 4 ). As a result, since lithium silicate is not generated when lithium is occluded in the negative electrode in the initial charging step, a reduction in discharge capacity is suppressed.
  • the pre-doping method for the negative electrode is not particularly limited, and a pre-doping method applied to a conventional lithium ion secondary battery is applicable.
  • the amount of lithium to be pre-doped is not particularly limited, and for example, it is preferably 1 to 4 times the molar amount of silicon oxide in the negative electrode active material layer.
  • Lithium ion secondary battery ⁇ 1st embodiment of the lithium ion secondary battery of this invention is equipped with the negative electrode mentioned above. For this reason, both the capacity development rate and the capacity maintenance rate when charging and discharging are repeated are high, and the charge / discharge characteristics are excellent.
  • the lithium ion secondary battery of the present embodiment may have a configuration similar to that of a conventional lithium ion secondary battery, for example, a configuration including a negative electrode, a positive electrode, and an electrolyte, except that the negative electrode described above is provided. If necessary, a separator may be provided between the negative electrode and the positive electrode.
  • the positive electrode constituting the secondary battery of the present embodiment is not particularly limited, and a known positive electrode used in a conventional lithium ion secondary battery can be applied.
  • a positive electrode active material, a binder and a solvent, and as necessary Accordingly, a positive electrode provided with a positive electrode active material layer formed using a positive electrode material containing a conductive additive or the like on a current collector (positive electrode current collector) can be exemplified.
  • Each material such as a binder, a solvent and a current collector constituting the positive electrode is not particularly limited, and examples thereof include the same materials as the binder, the solvent and the current collector constituting the negative electrode.
  • the conductive additive constituting the positive electrode is not particularly limited, and examples thereof include carbon black such as ketjen black and acetylene black, graphite (graphite), carbon nanotube (CNT), carbon nanohorn, graphene, fullerene and the like.
  • carbon black such as ketjen black and acetylene black
  • graphite graphite
  • carbon nanotube CNT
  • carbon nanohorn carbon nanohorn
  • graphene fullerene and the like.
  • One type of conductive auxiliary in the positive electrode may be used alone, or two or more types may be used in combination.
  • a metal acid lithium compound represented by a general formula “LiM x O y (wherein M is a metal; x and y are composition ratios of metal M and oxygen O)” can be exemplified.
  • metal acid lithium compound include lithium cobaltate (LiCoO 2 ), lithium nickelate (LiNiO 2 ), lithium manganate (LiMn 2 O 4 ), and the like, and olivine iron phosphate having a similar composition. Lithium (LiFePO 4 ) can also be used.
  • M may be a plurality of types of the lithium metal acid compound.
  • p + q + r x.
  • Specific examples include LiNi 0.33 Mn 0.33 Co 0.33 O 2 and the like.
  • the positive electrode active material one kind may be used alone, or two or more kinds may be used in combination.
  • Each content ratio of the positive electrode active material, the conductive additive and the binder with respect to the total mass of the positive electrode material can be the same as each content ratio of the negative electrode active material, the conductive additive and the binder constituting the negative electrode material.
  • the content ratio of optional components added as necessary can be the same as in the case of the negative electrode material.
  • the thickness of the positive electrode active material layer is not particularly limited, and may be about 10 to 100 ⁇ m, for example.
  • the production of the positive electrode active material layer can be performed in the same manner as in the case of the negative electrode active material layer except that a positive electrode material is used instead of the negative electrode material.
  • the electrolyte is not particularly limited, and for example, a known electrolyte, an electrolytic solution, and the like used in a known lithium ion secondary battery can be applied.
  • the electrolytic solution include a mixed solution in which an electrolyte salt is dissolved in an organic solvent.
  • organic solvent those having resistance against high voltage are preferable, for example, ethylene carbonate, propylene carbonate, dimethyl carbonate, ⁇ -butyrolactone, sulfolane, dimethyl sulfoxide, acetonitrile, dimethylformamide, dimethylacetamide, 1,2-dimethoxyethane,
  • polar solvents such as 1,2-diethoxyethane, tetrohydrafuran, 2-methyltetrahydrofuran, dioxolane, and methyl acetate, or a mixture of two or more of these solvents.
  • the electrolyte salt for example, in the case of a lithium ion secondary battery, LiClO 4 , LiPF 6 , LiBF 4 , LiAsF 6 , LiCF 6 , LiCF 3 CO 2 , LiPF 6 SO 3 , LiN (SO 3 CF 3 ) 2 , Li ( Examples thereof include salts containing lithium such as SO 2 CF 2 CF 3 ) 2 , LiN (COCF 3 ) 2, and LiN (COCF 2 CF 3 ) 2 , or a mixture of two or more of these salts.
  • the material which comprises a separator is not specifically limited, For example, a porous polymer film, a nonwoven fabric, glass fiber etc. are mentioned.
  • the thickness of the separator is not particularly limited as long as it can prevent a short circuit between the positive electrode and the negative electrode, and can be, for example, 0.1 ⁇ m to 10 ⁇ m.
  • the form of the lithium ion secondary battery of the present embodiment is not particularly limited, and examples thereof include a cylindrical shape, a square shape, a coin shape, a sheet shape, and a laminate shape. According to each form, a cell can be accommodated in a metal case, a resin case, etc.
  • the manufacturing method of the lithium ion secondary battery of this embodiment is not particularly limited, and a manufacturing method similar to that of a conventional lithium ion secondary battery can be applied in a glove box or in a dry air atmosphere as necessary.
  • Example 1 Silicon monoxide (SiO, average particle size 5.0 ⁇ m, 70 parts by mass), CNT (5 parts by mass), SBR (5 parts by mass), and polyacrylic acid (10 parts by mass) are put in a reagent bottle, and further distilled water. Was added to adjust the concentration, followed by mixing at 2000 rpm for 2 minutes using a self-revolving mixer. Acetylene black (5 parts by mass) and SMW (5 parts by mass) were added to this mixture, and the mixture was mixed at 2000 rpm for 2 minutes using a self-revolving mixer. This mixture was subjected to a dispersion treatment with an ultrasonic homogenizer for 10 minutes, and then this dispersion was again mixed for 3 minutes at 2000 rpm using a self-revolving mixer to obtain a negative electrode material.
  • the above SMW (official name: special-multi-walled CNT) is the conductive auxiliary agent B, and is a multi-walled carbon nanotube manufactured by Sigma-Aldrich.
  • the number of layers is 3 to 8, the average aspect ratio (B) is 450, the average diameter (outer diameter) is 10 nm, the average inner diameter is 4.5 nm, the average The length of is 4.5 ⁇ m.
  • the ratio ( ⁇ ) (5 ⁇ m / 0.01 ⁇ m) of the average particle diameter of SiO as an active material to 5.0 ⁇ m and the diameter of SMW of 10 nm is 500, and the average particle diameter of SiO is 5 ⁇ m and SMW.
  • the ratio ( ⁇ ) (5.0 ⁇ m / 4.5 ⁇ m) to the length of 4.5 ⁇ m is 1.1.
  • the above CNT is the conductive auxiliary agent A and is a carbon nanotube produced by a CVD method.
  • the average aspect ratio (A) is 400, the average diameter (outer diameter) is 12.5 nm, and the average length is 5 ⁇ m.
  • the ratio ( ⁇ ) (5 ⁇ m ⁇ 0.0125 ⁇ m) of the average particle diameter of SiO which is an active material to the diameter of CNT is 400, and the average particle diameter of SiO is 5 ⁇ m and the length of CNT
  • the ratio ( ⁇ ) of (5 ⁇ m / 5 ⁇ m) is 1.
  • NMP N-methylpyrrolidone
  • the positive electrode material was applied to both sides of an aluminum foil having a thickness of 15 ⁇ m using a bar coater, dried under reduced pressure at 100 ° C., 0.1 MPa for 10 hours, and then roll-pressed, whereby a current collector was obtained.
  • a positive electrode active material layer having a thickness of 60 ⁇ m was formed on the aluminum foil to obtain a positive electrode.
  • EC ethylene carbonate
  • DEC diethyl carbonate
  • GBL gamma butyrolactone
  • Example 2 A negative electrode and a lithium ion secondary battery were produced in the same manner as in Example 1 except that CNTs having an average length of 1 ⁇ m were used.
  • the aspect ratio (A) of CNT was 80, and the ratio ( ⁇ ) of the average particle diameter of 5 ⁇ m of SiO as an active material and the diameter of 12.5 nm of CNT (5 ⁇ m / 0.0125 ⁇ m) Is 400, and the ratio ( ⁇ ) (5 ⁇ m / 1 ⁇ m) between the average particle diameter of SiO of 5 ⁇ m and the length of CNT of 1 ⁇ m is 5.
  • Example 3 A negative electrode material, a negative electrode, and a lithium ion secondary battery were produced in the same manner as in Example 1 except that VGCF (registered trademark) having an average length of about 5 ⁇ m was used instead of CNT.
  • VGCF registered trademark
  • vapor grown carbon fiber having an average length of about 5 ⁇ m is a vapor grown carbon fiber manufactured by Showa Denko.
  • the average aspect ratio (A) is about 33, and the average diameter (outer diameter) is about 150 nm.
  • the ratio ( ⁇ ) (5 ⁇ m ⁇ 0.150 ⁇ m) of the average particle diameter of SiO as an active material to the diameter of VGCF (registered trademark) is about 33, and the average particle diameter of SiO
  • the ratio ( ⁇ ) (5 ⁇ m / 5 ⁇ m) between 5 ⁇ m and the length of VGCF (registered trademark) is 1.
  • Example 4 A negative electrode material, a negative electrode, and a lithium ion secondary battery were produced in the same manner as in Example 3 except that VGCF (registered trademark) having an average length of about 1 ⁇ m was used.
  • VGCF (registered trademark) (official name: vapor grown carbon fiber) having an average length of about 1 ⁇ m is a vapor grown carbon fiber manufactured by Showa Denko. Its average aspect ratio (A) is about 7, and its average diameter (outer diameter) is about 150 nm.
  • the ratio ( ⁇ ) (5 ⁇ m ⁇ 0.150 ⁇ m) of the average particle diameter of SiO as an active material to the diameter of VGCF (registered trademark) is about 7, and the average particle diameter of SiO
  • the ratio ( ⁇ ) (5 ⁇ m / 1 ⁇ m) between 5 ⁇ m and the length of VGCF (registered trademark) is 5.
  • Example 5 A negative electrode material, a negative electrode, and a lithium ion secondary battery were produced in the same manner as in Example 3 except that the average particle diameter of silicon monoxide was about 1 ⁇ m.
  • the ratio ( ⁇ ) (1 ⁇ m / 0.01 ⁇ m) of the average particle diameter of SiO, which is an active material, to 10 nm of SMW is 100, and the average particle diameter of SiO is 1 ⁇ m and the length of SMW is 4.5 ⁇ m.
  • the ratio ( ⁇ ) of (1 ⁇ m / 4.5 ⁇ m) is about 0.2.
  • the ratio ( ⁇ ) (1 ⁇ m ⁇ 0.150 ⁇ m) of the average particle diameter of SiO as an active material to the diameter of VGCF (registered trademark) is approximately 7, and the average particle diameter of SiO
  • the ratio ( ⁇ ) (1 ⁇ m / 5 ⁇ m) between 5 ⁇ m and the length of VGCF (registered trademark) is 0.2.
  • Example 6 instead of SMW, Flotube (a carbon nanotube manufactured by Seanano Corporation. Its average aspect ratio (B) is 800, its average diameter (outer diameter) is 12.5 nm, and its average length is A negative electrode material, a negative electrode, and a lithium ion secondary battery were produced in the same manner as in Example 3 except that these values were 10 ⁇ m.
  • the ratio ( ⁇ ) (5 ⁇ m / 0.0125 ⁇ m) of the average particle diameter of 5 ⁇ m of the active material SiO to the diameter of 12.5 nm of Flotube (5 ⁇ m / 0.0125 ⁇ m) was 400, and the average particle diameter of SiO
  • the ratio ( ⁇ ) (5 ⁇ m / 10 ⁇ m) between 5 ⁇ m and the length of the Flotube 10 ⁇ m is 0.5.
  • the aspect ratio (B) of Flotube is 800, and the ratio ( ⁇ ) (5 ⁇ m / 0.150 ⁇ m) of the average particle diameter of SiO as an active material is about 5 ⁇ m and the diameter of VGCF (registered trademark) is about 150 nm is about 33.
  • the ratio ( ⁇ ) (5 ⁇ m / 5 ⁇ m) of the average particle diameter of SiO of about 5 ⁇ m and the length of VGCF (registered trademark) of about 5 ⁇ m is 1.
  • Example 1 A negative electrode and a lithium ion secondary battery were produced in the same manner as in Example 1 except that CNT was not contained and SMW (10 parts by mass) was included.
  • Example 2 A negative electrode and a lithium ion secondary battery were produced in the same manner as in Example 1 except that SMW was not contained and CNT (10 parts by mass) was contained.
  • Example 3 A negative electrode and a lithium ion secondary battery were produced in the same manner as in Example 1 except that Flotube (5 parts by mass) was used instead of SMW.
  • the above Flotube is a carbon nanotube manufactured by Seanano. Its average aspect ratio (B) is 800, its average diameter (outer diameter) is 12.5 nm, and its average length is 10 ⁇ m. These numerical values are values measured by TEM.
  • the ratio ( ⁇ ) (5 ⁇ m / 0.0125 ⁇ m) between the average particle diameter of SiO as an active material of 5.0 ⁇ m and the diameter of Flotube of 12.5 nm is 400, and the average particle diameter of SiO is 5 ⁇ m.
  • the ratio ( ⁇ ) (5 ⁇ m / 10 ⁇ m) of the length of SMW to 10 ⁇ m is 0.5.
  • a negative electrode material, a negative electrode, and a lithium ion secondary battery were produced in the same manner as in Example 6 except that the average particle diameter of silicon monoxide was about 1 ⁇ m.
  • the ratio ( ⁇ ) (1 ⁇ m / 0.0125 ⁇ m) of the average particle diameter of SiO, which is the active material, to the diameter of 12.5 nm of the float tube is 80, and the average particle diameter of SiO is 1 ⁇ m and the float tube.
  • the ratio ( ⁇ ) (1 ⁇ m / 10 ⁇ m) to the length of 10 ⁇ m is 0.1.
  • the ratio ( ⁇ ) (1 ⁇ m / 0.15 ⁇ m) between the average particle diameter of 1 ⁇ m of the active material SiO and the diameter of VGCF (registered trademark) 150 nm is about 7, and the average particle diameter of SiO is 1 ⁇ m and VGCF (registered)
  • the ratio ( ⁇ ) (1 ⁇ m / 5 ⁇ m) to the length of 5 ⁇ m of the trademark is 0.2.

Abstract

Cette matière d'électrode négative comprend une matière active d'électrode négative, un assistant conducteur et un liant. L'assistant conducteur comprend un assistant conducteur A et un assistant conducteur B. L'assistant conducteur B est un carbone fibreux qui a un diamètre d'au moins 2 nm mais inférieur à 100 nm, et un rapport d'aspect (B) représenté par (longueur/diamètre) de 30 à 10 000. L'assistant conducteur B a une forme non linéaire différente de celle de l'assistant conducteur A. L'assistant conducteur A est un carbone fibreux qui a un diamètre d'au moins 1 nm mais inférieur à 1 000 nm, et un rapport d'aspect (A) représenté par (longueur/diamètre) de 1 à 10 000. L'assistant conducteur A a une forme qui est linéaire ou presque linéaire. Le rapport d'aspect (B) est supérieur au rapport d'aspect (A). Le diamètre de l'assistant conducteur A est supérieur au diamètre de l'assistant conducteur B. La matière active d'électrode négative est particulaire. Le rapport δ représenté par (la taille moyenne des particules de la matière active d'électrode négative/la longueur de l'assistant conducteur B) est de 0,15 à 10.
PCT/JP2016/079704 2015-10-05 2016-10-05 Matière d'électrode négative, électrode négative, et batterie rechargeable au lithium-ion WO2017061514A1 (fr)

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